Non-adhesive high elastic elastomer threads

ABSTRACT

Normally sticky segmented polyurethane threads are rendered nonadhesive by coating with a dressing agent comprising tertiary phosphoric acid ester of the formula   IN WHICH R1 and R2 are hydrocarbon radicals of the formula CnH2n 1 or CnH2n 1; n is 1 to 20; m is an integer of from 1 to 6; and R3 is hydrogen or methyl. The coating can optionally contain, as an additional ingredient, an ethylene oxide adduct of the formula

United States Patent [1 1 LenZ et al.

[ NOV. 6, 1973 NON-ADHESIVE HIGH ELASTIC ELASTOMER THREADS [75] Inventors: Hans Lenz, Dormagen; Joachim Kolbe, Leverkusen; Herbert Marzolph; Kurt Bernklau, both of Dormagen, all of Germany [73] Assignees Bayer Aktiengesellschait,

Lcverkusen, Germany [22] Filed: Oct. 28, I971 21 Appl. No.: 193,572

Related U.S. Application Data [63] Continuation of Ser. No. 788,335, Dec. 31, 1968,

abandoned.

[30] Foreign Application Priority Data Jan. 8, 1968 Germany P 16 69 432.9

[52] U.S. Cl. ll7/l38.8 D, 57/140 C, 57/153, 117/139.5 F, 117/1395 CQ, 161/175, 264/130 [51] Int. Cl D02g 3/36, 344d [[22 [58] Field of Search 117/139.5 F, 139.5 CF, 117/139.5 CQ, 138.8 D; 161/175; 8/115.6;

[56] References Cited UNITED STATES PATENTS 3,482,010 12/1969 Yasui et a1 117/138.8 D

1,970,578 8/1934 Schoeller et al. 117/1395 CQ 2,742,379 4/1956 Schofield 117/1395 CQ 2,842,462 7/1958 Haas 1 117/1395 CF 2,909,559 10/1959 Lanham 260/953 2,990,421 6/1961 Melton et al. 260/953 3,310,935 3/1967 Wurzbcrg et al. .1 57/164 3,407,150 10/1968 Wismcr et al 1 1 260/953 3,432,343 3/1969 Lcvinc 117/1395 (0 3,472,919 10/1969 Nagy et al 260/953 3,495,394 2/1970 Mohajer 57/153 Primary Examiner-William D. Martin Assistant ExaminerM. Sofocleous Attorney-Plumley and Tyner [57] ABSTRACT Normally sticky segmented polyurethane threads are rendered non-adhesive by coating with a dressing agent comprising tertiary phosphoric acid ester of the formula o o P in which R is a hydrocarbon radical of the-formula C l-1 or C 1-1 q is 10 to 20; and p is an integer of from 4 to 50.

3 Claims, No Drawings NON-ADHESIVE HIGH ELASTIC ELASTOMER THREADS This is a continuation of application Ser. No. 788,335 filed Dec. 31, 1968 now abandoned.

This invention relates to non-adhesive, highly elastic threads from polyurethane elastomers (segmented polyurethanes) to a dressing agent for adhesive, highly elastic'threads and to a process for dressing highly elastic and highly stretchable threads with specific dressing agents.

It is known that highly elastic threads, such as rubber threads or synthetic threads which are made of highly elastic, segmented polyurethanes can only be worked up without difficulty if a suitable dressing has first been applied to their surface. Highly elastic elastomer threads which have an elongation at break in the region of 400 to 800 percent and in which the fibre forming substance is a polymer in the form of a chain which consists of at least 85 percent of a segmented polyurethane have a much greater tendency to stick together than the so-called hard threads. These threads stick together in the thread package and their adhesion to other surfaces, for example to the surface of the thread guide elements, is also especially marked. Rubber threads are usually dressed with talcum, and this also may be used for elastomer threads made of highly elastic, segmented polyurethanes, although the talcum dust wich is easily rubbed off causes soiling and even damage to the textile machines used for the subsequent working up. It has therefore already been proposed to dress threads of highly elastic, segmented polyurethanes with textile oils such as mineral oil in whichcertain metal soaps are finely dispersed. The soaps used are preferably sodium, magnesium, zinc or aluminium salts of long chain fatty acids. These dispersions are preferably applied to the highly elastic threads during the spinning process. Polyamyl siloxanes are said to be advantageous for use as dressing agents for certain threads of highly elastic, segmented polyurethanes whilst in other cases an application or organic silicic acid esters such as tetrakis-(Z-ethylbutyl) silicate has proved to be satisfactory.

If only the so-called textile oils are used as dressing for highly elastic segmented polyurethane threads, this prevents sticking together to a small extent. Since these low viscosity oils diffuse fairly rapidly into the thread leaving little of the dressing on the surface of the thread, the thread packages remain non-sticky only when left to stand for relatively brief periods, especially if the packages are freshly wound and have not yet been treated.

It has now been found that thread packages of segmented polyurethane threads which have not been treated are still completely non-sticky after they have been left to stand for several days if a dressing which contains an alkylene oxide adduct of an phosphoric acid diester has been applied continuously before winding the threads. The phosphoric acid diesters-can be prepared by known methods both with saturated and with unsaturated alcohols and can then be reacted with alkylene oxide.

Tertiary phosphoric acid esters of the general formula R,o o

in which R and R denote a hydrocarbon radical of the formula C,,H or C,,l-l (n 1 to 20, m l to 6) and R represents a hydrogen atom or a methyl group, are suitable for use in the process according to the invention.

In order to increase the emulsifiability in the socalled textile oils on the one hand and the solubility in the washing liquors on the other hand, of the tertiary phosphoric acid esters, they may be mixed with emulsifying agents before they are applied. Ethylene oxide adducts of the general formula R (O CH CH OH in which R represents a hydrocarbon radical of the formula C H or C,,l-l (q= 10 to 20, p= 4 to 50) may be used for this purpose.

The quantities of ethylene oxide adduct which are added vary according to the constitution and nature of the tertiary phosphoric acid ester used.

The tertiary phosphoric acid esters are non-ionic compounds and therefore ensure that the polyurethane elastomer threads do not affect the ionic activity of the brightening agents for mixed fibres and of the detergents and certain dyes. This means that precipitation with other dressing agents, detergents or dyes are not to be expected.

After the tertiary phosphoric acid esters have been mixed with emulsifying alkylene oxide adducts, they are dispersed, or preferably dissolved, in so-called textile oils, e.g. mineral oil in concentrations of between 10 and 90 percent, depending on the particular requirements. The mixtures so obtained are liquid to pasty at room temperature and are frequently even of a waxy consistency, depending on the nature and proportions of the phosphoric acid ester, emulsifying agent and oil used. If the viscosity of such a mixture is too high, a solvent which is inert to the elastomer substrate may be added. Alternatively, according to a preferred procedure, the dressing mixture is applied at elevated temperature by means of rollers which dip into heated vats. In certain cases, the phosphoric acid esters may be applied to the threads without any further additives and if desired in the form of a melt. In order to prevent the segmented polyurethane filaments from subsequently sticking together in the thread package, the elastomer threads should contain an amount of phosphoric acid ester equal to 0.5 to 10 percent and preferably 1 to 5 percent of their own weight.

This treatment enables the production of highly elastic elastomer threads which are non-sticky in the pack age even when packages of higher weight are produced, and which therefore will run off the package smoothly even after prolonged storage. The application of the dressing according to the invention ensures that smoothness of the thread surface which is necessary for further working up, ensures adequate protection against the accumulation of electrostatic charges and causes practically no alteration in the properties, especially the physical properties such as the capacity for elastic recovery of the threads.

The elastomer threads can be produced by known procedures from spinning solutions of segmented polyurethanes, e.g. according to German Patent Specification No. 1,123,467 or according to German Auslegeschriften Nos. 1,183,196 and 1,161,007. The following examples illustrate more particularly the invention.

Example 1 A solution of the following composition:

20 parts by weight of adduct of 1 mol of distearylphosphate and 2 mols of ethylene oxide,

parts by weight of adduct of 1 mol of stearyl alcohol and 30 mols of ethylene oxide,

70 parts by weight of paraffin oil of viscosity 35 to 45 cP/C is applied to the elastomer filaments which have been spun from dimethylformamide (produced according to German Patent Specification No. 1,123,467) after they have left the spinning shaft, using dressing rollers which dip into vats which are heated to 65C.

The total titre of the threads is 400 den and the amount of dressing applied, which is determined by extraction with carbon tetrachloride, is 5 percent of the weight of the thread. Even after the spinning spool has been left to stand for 8 days, the layers of thread on the package have not stuck together and the thread can be rewound without any increased thread tensions and consequently any marked stretching of the highly elastic thread taking place.

Example 2 A solution of the following composition: 24 parts by weight of adduct of 1 mol of die-oleyl phosphate and 2 mols of ethylene oxide, 6 parts by weight of adduct of 1 mol of oleyl alcohol and 20 mols of ethylene oxide, 70 parts by weight of paraffin oil of viscosity 35 to 45 cP/20C is applied to the spun elastomer threads after they have left the spinning shaft, using dressing rollers which dip into vats heated to 60C. The total titre of the thread is 400 den and the amount of dressing applied, which is determined by extraction with carbon tetrachloride, is 7 percent of the weight of the thread. The layers of thread on the package are not stuck together even after the spinning spool has been left to stand for 8 days, and the thread can be rewound without increased thread tensions and hence any marked stretching of the highly elastic thread taking place.

Example 3 A solution of the following composition: 20 parts by weight of adduct of 1 mol of di-ioctylphosphate and 2 mols of ethylene oxide, 10 parts by weight of adduct of 1 mol of lauryl alcohol and 5 mols of ethylene oxide, is applied to the spun elastomer threads after they leave the spinning shaft, using dressing rollers.

The total titre of the thread is 400 den and theamount of dressing applied, which is determined by extraction with carbon tetrachloride, is l0 percent, based on the weight of the thread. The layers of thread on the package are not stuck together even after the spinning spool has been left to stand for 4 days, and the thread can be rewound without any increased thread tensions and therefore marked stretching of the highly elastic thread taking place.

What we claim is:

l. A non-adhesive highly elastic thread comprising a normally sticky segmented polyurethane elastomer having a coating consisting essentially of 0.5 to 10 percent by weight based on the weight of the elastomer thread of a tertiary phosphoric acid ester of the formula R-,() (()(2H;,R;,),()H

in which R and R are hydrocarbon radicals of the formula n 2n+I n zrhli n is l to 20;

m is l to 6; and

R is hydrogen or methyl.

2. The non-adhesive highly elastic thread of claim 1 wherein said coating consists essentially of a tertiary phosphoric acid ester of the formula R O l u ulmOH in which R and R are hydrocarbon radicals of the formula n 2n+1 or n 2nl;

n is l to 20;

m is 1 to 6; and

R is hydrogen or methyl; and an ethylene oxide adduct of the formula in which R is a hydrocarbon radical of the formula q 2q+l or q 2ql;

q is 10 to 20; and

p is 4 to 50.

3. The non-adhesive highly elastic thread of claim 1 in which said polyurethane elastomer has an elongation at break of 400 to 800 percent and which consists of at least percent of a segmented polyurethane elastomer. 

2. The non-adhesive highly elastic thread of claim 1 wherein said coating consists essentially of a tertiary phosphoric acid ester of the formula
 3. The non-adhesive highly elastic thread of claim 1 in which said polyurethane elastomer has an elongation at break of 400 to 800 percent and which consists of at least 85 percent of a segmented polyurethane elastomer. 